Reaction product of aldehydes and triazine derivatives



' halo-hydrocarbon radicals, R

Patented July 20, 1943 UNITED STATES PATENT OFFICE- REAC'I ION PRODUCTOF ALDEHYDES AND TRIAZINE DERIVATIVES Gaetano F. DAlelio, Pittsileld,Mas's., assignor to General Electric Company, a corporation of New YorkNo Drawing. Application July 29, 1942,

SerialNo. 452,790

20 Claims.

This invention relates to the production of new synthetic materials andmore particularly to new reaction products of particular utility in theplastics and coating arts. Specifically the invention isconcerned withcompositions of matter comprising a condensation product. of ingradientscomprising an aldehyde, including polymeric aldehydes, hydroxyaldehydesand aldehyde-addition products, e. g., formaldehyde, I paraformaldehyde,vdimethylol urea, trimethylol melamine, aldol, glycollic aldehyde, etc.,and a triazine derivative corresponding to the following generalformula: a

where n represents an integer and is at least 1 and not. more than 2, Zrepresents a member of the class consisting of oxygen and sulfur, Rrepresents a member of the class consisting of hydrogen and monovalenthydrocarbon and substituted hydrocarbon radicals, more particularlyIllustrative examples of monovalent radicals that R in the above formulamay represent are: aliphatic- (e. g., methyl, ethyl, propyl, isopropyl,

butyl, secondary butyl, isobutyl, butenyl, amyl,v

isoamyl, hexyl,'octy1, methallyl, ethallyl, crotyl, etc), includingcycloaliphatic (e. g., cyclopentyl, cyclopen'tenyl, cyclohexyl,cyclohexenyl, cyclohepty'l, etc); aryl (e. g., phenyl, diphenyl orxenyl, naphthyl, etc.); aliphatic-substituted aryl (e. g., tolyl, xylyl,ethylphenyl, propylphenyl, isoprcpylphenyl, allylphenyl,Z-butenylphenyl, tertiary-butylphenyl, etc.); aryl-substituted aliphatic(e. g., benzyl, phenylethyl, phenylpropyl, phenylisopropyl, cinnamyl,etc.); and their homologues, as well as those groups wlth one or; more'of their hydrogen atoms substituted by, for example, a. halogen.Specific examples of halogeno-substituted. hydrocarbon radicals arechloromethyl, chloroethyl, chlorophenyl, di-

chlorophenyl, chlorocyclohexyl, ethyl chlorophenyl, phenyl chloroethyl,bromoethyl, brornopropyl, fiuorophenyl, iodophenyl, bromotolyl, etc.Preferably R in Formula I is hydrogen However, there also may be used incarrying the present invention into eflect compounds such, for instance,as those represented by the general formulas: i

- and, more, particularly,

represents a where n, Z, R, R and X have the same meanings as givenabove with reference to Formula I.

Illustrative examples of divalentradlcals that R in the above, formulasmay represent are: di-

- valent aliphatic, e.- g., ethylene, propylene (trimethylene),propenylene, butylene, isobutylene,

pentylene, isopentylene, etc.. including divalent cycloaliphatic, e. g.,cyclopentylene, cyclopentenylene, cyclohexylene, cyclohexenylene,cycloheptylene, etc.; divalent aromatic, e. g,. phenylene, xenylene,naphthylene, etc.; divalent aliphaticsubstituted aromatic, e. g.,2,4-to1ylene, ethyl, 2,5-phenylene,.isopropy1 3,4-phenylene, 1-butyl2,4-naphthylene, etc.; divalent aromatic-substituted' aliphatic, e. g.,phenylethylene, phenylpropylene,naphthylisobutylene, xylylene, alpha-(4-tolylene) beta'-butyl, etc.; radicals that may be classed either asdivalent aliphatic-substituted aromatic or divalent aromatic-substitutedaliphatic, e. g., 4,alpha-to1ylene, 3,beta-phenyleneethyl, 4,alpha-'xy1ylene, 2,gamma phenyienebuty1,etc.; and their homologues, as wellas those divalent radicals with one or more of their hydrogen atomsreplaced by a substituent, e. g., halogeno, amino, acetyl, acetoxy,carcoalkoxy, alkoxy, aryloxy, hydroxy, alkyl, alkenyl, etc. Specificexamples of substituted divalent radicals are chloroethylene,chloropropylene, bromobutylene, chlorophenylene, chlorotolylene,bromophenylene, chloronaphthylene, bromonaphthylene, bromo 1,4-tolylene,chlorocyclopentylene, chloroc y c l o p e n t e n ylene,carbomethoxyphenylene, ethoxyphenylene, acetophenylene,acetoxyphenylene, bromocyclopentylene, aminophenylene, phenoxyphenylene,methylphenylene (tolylene), allylphenylene, etc. Preferably R isethylene, phenylene or tolylene.

Instead of the symmetrical triazines(s-triazines) represented by theabove formulas, corresponding derivatives of the asymmetrical triazlnesor of the vlcinal triazines may be used.

The triazine derivatives that are used in carry ing the presentinvention into effect are more fully described and are specificallyclaimed in my above-identifled parent copending application Serial No.432,659. As ointed out in this copending application, a method ofpreparing the triazine derivatives used in practicing the presentinvention comprises effecting reaction between a bis-(halogenoaliphatic-amido)-substituted divalent compound, more particularly adivalent hydrocarbon or halo-hydrocarbon, or a bis- (halogencaliphatic-thionoamido) -substituted divalent compound and a mercaptodiamino [(-NHR)2] s-triazine in the presence of a hydrohalide acceptor,e. an, an alkali-metal hydroxide, the reactants being employed in theratio of one mol of the mercapto diamino s-triazlne per moi of the saidsubstituted divalent compound.

Examples of triazine derivatives embraced by Formula I that may be usedin producing the new condensation products or the present'invention arethe (diaminos triazinyl thio acetamido) (halogeno acetamido)-substitutedaliphatic hydrocarbons, more particularly the (diamino striazinyl thioacetamido) (chloroacetamido) alkanes, e. g., alpha-(diamino s-triazinylthio acetamido) beta-(chloroacetamido) ethane, alpha- (diaminos-triazinyl thio acetothionoamido) beta-(chloroacetothionoamido) ethane,the (diamino s-triazinyl thio acetamido) (halogenoacetamido)-substituted aromatic hydrocarbons, e. g., the (diaminos-triazinyl thioacetamido) (chloroacetamido) benzenes, the (diaminos-trlazinyl thio acetothionoamido) (chloroacetothionoamido) benzenes,the (diamino s-triazinyl thio acetamido) (chloroacetamido) toluenes,etc.

More specific examples of triazine derivatives that may be employed inproducing my new condensation products are listed below:

(Diamino s-triazinyl thio acetamido) (chloroacetamido) propanes (Diaminos-triazinyl thio acetothionoamidol (chloroacetamido) (bromoacetamido)(bromoacetamido) (bromoacetamido) (chloro- (iodoacetamido) cyclopentaneschloro- (chloro- (bromo- Alpha-(diamino s-triazinyl alpha'-thiopropanamido) ethane Alpha-(diamino s-triazinyl beta'-thio propanamido)beta (beta" chloropropanamido) ethane beta (alpha" chloropropanamido) PAlpha-(diamino s-triazinyl alpha'-thio propanthionoamido)beta-(beta"-chloro propanthi onoamido) ethane (Diamino s-triazinylalpha-thio propanamido) (alpha-br0mo propanamido) propanes (Diaminos-triazinyl beta-thio propanamido (beta'-bromo propanamido) propanes(Diamino s-triazinyl alpha-thio propanamido) (a1pha'-chloro propanamido)benzenes (Diamino s-triazinyl beta-thio propanamido) (beta'-iodopropanamido) toluenes (Diamino s-triazinyl alpha-thio propanamido)(alpha'-chloro propanamido) naphthalenes (Diamino s-triazinyl beta-thiopropanamido) (beta-chloro propanamido) chlorobenzenes (Diaminos-triazinyl alpha-thio propanamido) alpha-fiuoro propanamido) octanesAlpha-(4,6-di- [methylamino] s-triazinyl-Z thio methylacetamido) gamma-(bromo methyl acetamido) propene' (4,6-dianilino s-triazinyl-2 beta-thioalphamethyl propanamido) (alpha'-methyl betachloro propanamido)chlorolsobutanes (4,6-di- [propylamino] s-triazinyl-Z beta-thioalpha-phenyl beta-pentyl propanamido) (alpha'-phenyl beta'-pentylbeta'-chloro propanamido) isopentanes (i-hexylamlno fi-xenylaminos-trlazinyl-Z, beta. thio propanamido) (beta-bromo propanamido) benzenes4-(4f-bromotoluido 6-benzylamino s-triazinyl-2' thio cyclo-hexenylacetothionoamido) 2- (cyclohexenyl chloro acetothionoamido)chlorotoluene 4-(4'-phenylchloroethylamino 6'-phenethylaminos-triazinyl-2' beta-thio propanamido) 3-(beta'-iodo propanamido)ethylbenzene It will be understood, of course, by those skilled in theart that, in those compounds listed above that are generically named,the described substituent groupings may be attached to any two positionsof the divalent compound represented by R in Formula I.

The present invention is based on my discovery that new and valuablematerials of particular utility in the plastics and coating arts can beproduced by effecting reaction between ingredients comprisingessentially an aldehyde; including polymeric aldehydes, hydroxyaldehydesand aldehyde-addition products, and a triazine derivative of the kindembraced by Formula I, numerous examples of which have been given aboveand in my above-identified parent copending application Serial No.432,659.

Resins heretofore have been made by condensing an aldehyde with athioammeline ether such, 1'01- example, as a bisthioammelinepolyalkylene ether, but such resins are not entirely satisfactory foruse in many applications, for instance in the production of moldingcompoundshaving a high plastic flow during molding combined with a rapidcure to an insoluble, infusible state. Surprisingly it was found thatthe heatecurable resinous condensation products of this invention andmolding compositions made therefrom show excellent flow characteristicsduring a short curing cycle. This is a property that is particularlydesirable in a thermosetting resin and molding compound. The moldedarticles have a high dielectric strength and excellent resistance toarcing. They have a good surface finish and outstanding resistance towater, being better, in general, than the ordinary urea-formaldehyderesins in this respect. The cured resins have a high resistance to heatand abrasion and, therefore, are especially suitable. for use whereoptimum heatand abrasion-resistance are properties of primaryimportance.

In practicing my invention the initial condensation reaction may becarried out at normal or at elevated temperatures, at atmospheric,subatmospheric or super-atmospheric pressures, and, under neutral,alkaline or acid conditions. Preferably the reaction between thecomponents is initiated under alkaline conditions.

cium hydroxides, mono-, dior tri-amines, etc. In some cases it isdesirable to cause the initial wcondensation reaction betweenthecomponents to take place in the presence of a primary condensationcatalyst and a secondary condensation catalyst. The primary catalystadvantageously is either an aldehyde-non-reactable nitrogencontainingbasic tertiary compound, e. g., tertiary amines such as trialkyl (e. g.,trimethyl, triethyl, etc.) amines, triaryl (e. g., triphenyl, tritolyl,etc.) amines, etc., or an aldehyde-reactable nitro-' gen-containingbasic compound, for instance ammonia, primary amines (e. g., ethylamine, propyl amine, etc.) and secondary amines (e. g., dipropyl amine,dibutyl amine, etc.) The secondary condensation catalyst, whichordinarily is used in an amount less than the amount of the primaryatalyst, advantageously is a fixed alkali, for intance'a carbonate,cyanide or hydroxide of an alkali metal (e. g., sodium, potassium,lithium, etc). Illustrative examples of acid condensation "catalyststhat may be employed are inorganic or rganic acids such as hydrochloric,sulfuric, phosphoric, acetic, lactic, acrylic, malonic, etc., or acid[salts such as sodium acid sulfate, monosodium hosphate, -monoso diumphthalate, etc. Mixtures of acids, of acid salts or of acids and of acidsalts may be employed if desired.

The reaction between the aldehyde, e. g., formldehyde, and the triazinederivative may be carried out in the presence of solvents or diluents,li'lllers, other natural or synthetic resinous bodies, r while admixedwith other materials that also can react with the aldehydic reactant orwith e triazine derivative, e. g., ketones, urea NHzCONH-i) thiourea,selenourea, iminourea iguanidine) substituted ureas, thioureas,selenoareas and iminoureas, e. 3., urea derivatives such as mentioned inmy Patent No. 2,285,418, issued June 9, 1942, page 1, column 1, lines41-49; mono- ;arnides of monocarboxylic and polycarboxylic cids andpolyamides of polycarboxylic acids,

e. g., acetamide, halogenated acetamides (e. g., a chlorinatedacetamide), maleic monoamide, malonic 'monoamide, phthalic monoamide,maleic -diamide, fux'naric diamide, malonic diamide,

itaconic diamide, the monoamide, diamide and triamide oftricarballylicacid, etc.,; aldehydereactable triazines other than thetriazine derivatives constituting the primary components of the resinsof the present invention, e. g., melamine, ammeline, ammelide, melem,melam, melon, numerous other examples being given in various copendingapplications'of mine, for instance in application Serial'No. 377,524,filed February 5, 1941; and in applications pending application;aminodiazines; phenol and substituted phenols, 1 e. g., the cresols, thexylenols, the tertiary alkyl phenols and numerous other phenols such asmentioned in my Patent No. 2,239,441; monohydric and polyhydric alco-Any substance yielding an alkaline or an acid 7 hols, e. g., butylalcohol alcohol, ethylene glycol, glycerine, polyvinyl alcohol, etc.:amines, including aromatic amines, e. g., aniline, etc.; and the like.

The modifying reactants may be incorporated with ,the triazinederivative and the aldehyde by mixing all the reactants and effectingcondensationtherebetween or by various permutations of reactants asdescribed, for example, in my Patent No. 2,281,559, issued May 5, 1942,with particular reference to reactions involving a nonhaloacylated urea,a halogenated ,acylated urea amyl alcohol, isoamyl and an aliphaticaldehyde (page 2, column I,

lines 4969) For instance, I may form a partial condensation product ofingredients comprising (1) urea or melamine or urea and melamine, (2) atriazine derivative of the kind embraced by Formula I, for example a(diamino s-triazinyl thio acetamido) (halogeno acetamido) -substitutedaliphatichydrocarbon, more particularly a (diamino s-triazinyl thioacetamido), (halogeno acetamido) alkane such, for instance, as alpha(diamino s-triazinyl thio acetamido) beta- (chloroacetamido) ethane,etc., a (diamino s-triazinyl thio acetamido) (halogeno acetamido)-substituted aromatic hydrocarbon, e. g., a (diamino s-triazinyl thioacetamido) (halogeno acetamido) benzene, a (diamino s-triazinyl thioacetamido) (halogeno acetamido) toluene, etc., and (3) an aldehyde,including polymeric aldehydes. hydroxyaldehydes and aldehyde-additionproducts, for instance, formaldehyde, paraformposition.

Some of the condensation products of this invention are thermoplasticmaterials even at an advanced stage of condensation while others arethermosetting or potentially thermosetting bodies that convert underheat or under heat and pressure to aninsoluble, infusible state. Thethermoplastic condensation products are of partlcular value asplasticizers for other synthetic resins. The thermosetting orpotentially thermosetting resinous condensation products, alone or mixedwith fillers, pigments, dyes, lubricants, plasticizers, curing agents,etc., may be used, for example, in the production ofmoldingcompositions.

The liquid intermediate condensation products oi this inventionmay beconcentrated or diluted further by the removal or addition of volatilesolvents to form liquid coating compositions of referred to in saidcoctand, for I example, a curing reactant, specifically a chlorinatedacetamide, to obtain a heat-curable comj adjusted viscosity andconcentrations. The heatconvertible or potentially heat-convertibleresinous condensation products may be used in liquid state, for instanceas surface-coating materials, in the production of paints, varnishes,lacquers, enamels, etc., for general adhesive applications, in producinglaminated articles'and for numerous other purposes. The liquidheat-hardenable or potentially heat-hardenable condensation productsalso may be used directly as casting resins, while those which are of agel-like nature in partially condensed state may be dried and granulatedto form clear, unfilled heat-convertible resins.

In order that those skilled in the art better may understand how, thepresent invention may be carried into efiect, the following examples aregiven by way of illustration and not "by way of limitation. All partsare by weight.

were heated together under reflux at the boiling temperature of the massfor 15 minutes, yielding a clear, resinous syrup. This syrup was mixedwhile hot with 33 parts alpha cellulose in flock form and 0.2 part of amold lubricant. specifically zinc stearate. The resulting wet moldingcomposition was divided into two equal parts. To one portion was added1.3 parts chloroacetamide (monochloroacetamide) and the mixture, thenwas ground in a mortar until a homogeneous mass resulted. Both portionsof molding compound were now dried at room temperature until sufficientmoisture had been removed to provide a material that could be moldedsatisfactorily. Samples of the dried and ground molding compositionswere molded at 140 C. under a pressure of 6,750 pounds per square inch.\The sample containing the chloroacetamide was molded for 5 minutes andthe other sample, for 7 minutes. In both cases well-cured molded pieceshaving well-knit and homogeneous structures were obtained. Both piecesshowed very good resistance to water as evidenced by the fact that, whenimmersed in boiling water for minutes followed by immersion in coldwater for 5 minutes, the molded piece made from thechloroacetamidecontaining molding compound absorbed only 3.7% by weightof water while the other molded piece absorbed only 3.9% by weight ofwater. (When similarly tested for water resistance, molded articles madefrom the ordinary ureaformaldehyde molding compositions absorb about5-'7% by weight of water.) The molding compounds showed very goodplastic flow duringmolding as indicated by the amount of flash on themolded piece.

Example 2 Parts Alpha-(diamino s-triazinyl thio acetamido)beta-(chloroacetamido) ethane 31. 9

(approx. 37.1

were placed in a flask which, in turn, was shaken at room temperaturefor 8 hours and then was allowed to stand undisturbed at roomtemperature for approximately 16 hours. The reaction product was in theform of a clear, light pink solution that was quite viscous. When asample of this syrupy condensation product was heated on a C. hot plate,it bodied slowly to a. flexible, infusible sheet that showed goodplastic flow during curing to the infusible state.

Example 3 Parts Alpha-(diamino s-triazinyl thio acetamido)beta-(chloroacetamido) ethane 31.9 Urea 30.0

Aqueous formaldehyde (approx. 37.1%

HCHO) 123.0 Aqueous ammonia (approx. 28% NHa) 3. 5

Aqueous solution of sodium hydroxide were heated together under refluxat the boiling Example 4 Same as Example 3 with the exception that themixed ingredients were heated together under reflux for only 25 minutes,after which 2 parts chloroacetamide were added and refluxing wascontinued for an additional 5 minutes. The chloroacetamide functions asa curing reactant. A well-cured molded piece having a'well-knit andhomogeneous structure was obtained. Its water resistance was somewhatbetter than the molded article of Example 3. It absorbed only 3.4% byweight of water when tested for its water resistance as described underExample 1.

Instead of using, chloroacetamide as above described, heat-convertiblecompositions may be produced by adding to the partial condensationproduct (in syrupy or other form) direct or active curing catalysts (e.g., citric acid, phthalic anhydride, malonic acid, oxalic acid, etc.).or latent curing catalysts (e. g., sodium chloroacetate, N- diethylchloroacetamide, glycine ethyl ester hydrochloride, etc.), or byintercondensation with curing reactants other than monochloroacetamide(e. g., diand tri-chloroacetamides, chlo roacetonitriles, alpha,beta-dibromopropionitrile, aminoacetamide hydrochloride, ethylenediamine monohydrochlor'ide, the ethanolamine hydrochlorides, nitrourea,chloroacetyl urea, chloroacetone, glycine, sulfamic acid, citricdiamide, phenacyl chloride, etc.). Other examples of curing reactantsthat may be employed to accelerate or to effect the curing of thethermosetting or potentially thermosetting resins of this and otherexamples are given in various copending applications of mine, forinstance in copending applications Serial No. 346,962, filed July 23,1940, and Serial No. 354,395, filed August 27, 1940, both of whichapplications are assigned to the same assignee as the present invention.

Example Parts Urea 60.0

Alpha-(diamino striazinyl thio acetamido) beta-(chloroacetamido) ethane8.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 4 134.0 Aqueous ammonia (approx. 28% MHz) 3.5 Aqueous solution ofsodium hydroxide were heatedtogether under reflux at the boilingtemperature of the mass for minutes, yielding a syrupy intercondensationproduct that bodied to a potentially thermosetting resin when a ample ofit was heated on a 140 C. hot plate. Chloroacetamide, glycine, sulfamicacid, phthalic anhydride and other curing agents such as mentioned underExample 4 accelerated the conversion of the resin to a cured orinsoluble and infusible state. v

Example 6 Parts Alpha-(diamino s-triazinyl thio acetamido)beta-(chloroacetamido) ethane 31.9 Melamine 63.0 Aqueous formaldehyde(approx. 37.1%

HCHO) 157.0 Aqueous ammonia (approx. 28% NHa)- 4.0 Aqueous solution ofsodium hydroxide Chloroacetamide 1.8

Allof the above ingredients with the exception of-the chloroacetamidwere heated together under reflux at the boiling temperature of the massfor 10 minutes, yielding a clear, syrupy condensation product. Thissyrup was mixed with 86 parts alpha cellulose, 0.4 part zinc stearateand the above-stated amount of chloroacetamide to iorm a moldingcompound. The wet molding composition was dried at room temperature forabout 16 hours. A sample of the dried and ground molding compound wasmolded for 5 minutes at 140 C. under a pressure of 6,750 pounds persquare inch. The molded piece was removed hot from the mold and did notwarp or become distorted upon cooling to room temperature. It was wellcured throughout and had a well-knit and homogeneous structure. It hadexcellent resistance to water'as shown by the fact that it absorbed only0.93 by weight of water when tested Example 8 P Alpha-(diaminos-triazinyl thio acetamido) beta-(chloroacetamido) ethane 31.0Trimethylol melamine (crystalline) 86.0 'Aqueous formaldehyde (approx.37.1%

HCHO) 5 35.0 V Aqueous ammonia (approx. 28% NH:) 3.0

Aqueous solution of sodium hydroxide (0.5 N) 2.5 Chlornareiuuhinln 7 1,5. Water 60.8,

for its water resistance as described under Example 1. The moldingcompound showed excellent flow duringmolding as evidenced by the amountof flash on the molded piece.

sulting resinous syrup was mixed with parts alpha cellulose and 0.3 partzinc stearate to form a molding compound. The wet molding compositionwas dried at room temperature until sumcient moisture had-been removedto provide a materialthai; could be molded satisfactorily. A well-curedmolded piece having a well-knit and homogeneous structure was obtainedby molding a sample or the dried and ground molding com pound for 5minutes at 140 C. under a pressure of 6,750 poundsper square inch. Itabsorbed only 4.1% by weight of water when tested for its waterresistance as described under Example- 1. The molding compound showedgood plastic flow during molding. f

All of the above ingredients with the exception of the chloroacetamidewere heated together under reflux at the boiling temperature of the massfor 8 minutes. A molding composition was made from the resultingresinous syrup by mixing therewith 75 parts alpha cellulose, 0.4 part.

zinc steal-ate and the above-stated amount of chloroacetamide. The wetmolding compound was dried as described under Example 7. A

well-cured molded piece was obtained by molding a sample of the driedand ground molding: compound for 5 minutes at 140 C. under a pressure of6,750 pounds per square inch. It had a, well-knit and homogeneousstructure and excellent resistance to water as shown by the fact that itabsorbed only 1.1% by weight of water when tested for its waterresistance as described under Example 1. The plastic flow of the moldingcompound during molding was very good.

Example 9 Parts Alpha-(diamino s-triazinyl thio acetamido)beta-(chloroacetamido) ethane 15.9 Acr 28.0

Aqueous solution of sodium hydroxide (0.5 N) Water 20.0

The above ingredients were mixed together.

the acrolein being added last. The mixture was heated gently underreflux at boiling temperature for5 minutes. yielding a heat-curableresinous syrup that slowly hardened to an infusible state when a sampleof the syrup was heated on a 140 C. hot plate. The resin showedexcellent plasticity during its conversion under heat to an infuslblestate. The product of this example would be suitable for use in theproduction of molding compounds.

Example 10 V Parts Alpha- (dlamino s-triazinyl thio ac'etamido)beta-(chloroacetamido)ethane 15.0 Furfur 48.0. Aqueous ammonia (approx.28% NH:) 1.0

Aqueous solution of sodium hydroxide were heated together under refluxat the boiling temperature of the mass for 14 minutes, yielding a darkbrown, resinous syrup. This syrup formed a hard, well-cohered, infusiblesheet when a sample of it was heated on a 140 C. hot plate. The resinousmaterial of this example may be used in the production of moldingcompounds or as a modifier of synthetic resins of inadequate flowcharacteristics to improve their plasticity.

Example 11 I Parts Alpha-(diamino s-triazinyl thio acetamido)beta-(chloroacetamido) ethane 15.9 Butyl alonhnl 37.9 Aqueousformaldehyde (approx. 37.1%

(HCHO) 40.5 Aqueous ammonia (approx. 28% NHa) 1.0

Aqueous solution of sodium hydroxide were heated together under refluxat the boiling temperature of the mass for minutes,

yielding a clear, syrupy intercondensation product. This syrup wasdehydrated by heating on a steam plate. The dehydrated syrup was solublein dioxane, butyl alcohol, ethylene glycol, ethylene glycol monoethylether and other organlc solvents. Glass plates were coated with samplesof the dehydrated syrup and the coated .plates were baked for severalhours at 70 C.

The baked coatings were hard, transparent, water-white, water-resistantand smooth, and adhered tightly to the glass surface. The solubility andfilm-forming characteristics of the resinous composition of this examplemake it especially suitable for use in the preparation of coating andimpregnating compositions. For .example, it may be used in theproduction of spirit and baking varnishes. It may be .used as a modifierof varnishes oi the aminoplast and alkyd-resin types. i

Example 12 Parts Alpha-(diamino s-triazinyl thio acetamido)beta-(chloroacetamido) ethane 15.9 Diethyl malonate 8.0

Aqueous formaldehyde (approx. 37.1%

HCHO). 81.0 Aqueous ammonia (approx. 28% NHa) 1.0 Aqueous solutionofsodium hydroxide were heated together under reflux at the boilingtemperature of the mass for 15 minutes, yielding a clear, resinoussyrup. This syrup bodied to a thermoplastic resin when a sample'of itwas heated on a 140 C. hot plate.

Example 13 v Parts Alpha-(diamino s-triazinyl thio acetamido)beta-(chloroacetamido) ethane 15.9, Acetamide 30.0 Aqueous formaldehyde(approx. 37.1%

(HCHO) 81.0 Aqueous ammonia (approx. 28% N113)..- 1.0 Aqueous solutionof sodium hydroxide o a curing agent.

Example 14 Parts Alpha-(diamino s-triazinyl thio acetamido)"beta-(chloroacetamido) ethane 15.9 5 Glycerine 4.6

Aqueous formaldehyde (approx. 37.1%

(HCHO) 81.0 Aqueous ammonia (approx. 28% NHa) v 1.0

Aqueous solution of sodium hydroxide 10 (0.5 N) 1.0

were heated together under reflux at the boiling temperature of the massfor 15 minutes, yielding a clear, resinous syrup. This syrup wasdehydrated by heating it on a hot plate. The dehydrated syrup wassoluble in dioxane, ethylene glycol, ethylene glycol monoethyl ether,butyl alcohol and other organic solvents. A glass plate was coated witha sample of the dehydrated particularly suitable for use in thepreparation of coating and impregnating compositions.

Example 15 Aqueous ammonia (approx. 28% NHs) 1.0 Aqueous solution ofsodium hydroxide (0.5 N) 1.0

Water 20.0

were heated together under reflux at the boiling temperature of the massfor 10 minutes, yielding a resinous syrup that bodied to a rubbery,seml-infusible state when a sample of it was heated on a 140 C. hotplate in the absence of The addition of chloroacet amide, glycine,sulfamic acid or other curing agent such as mentioned under Example 4 tothe resinous syrup, followed by heating on a 140 C. hot plate, resultedin the curing of the syrup to an infusible resinous mass. The resinouscomposition of this example is suitable for use in the production ofmolding compounds or it may be used in the preparation of variouscoating and impregnating compositions.

It will be understood, of course, by those skilled in the art that thereaction between the components may be effected at temperatures ranging,for example, from room temperature to the fusion or boiling temperatureof the mixed reactants or of solutions of the mixed reactants, thereaction proceeding more slowly at normal temperatures than at elevatedtemperatures in accordance with the general law of chemical reactions.Thus, instead of effecting reaction between the ingredients of Examples1 and 3 to 15, inclusive, at boiling temperature as mentioned in theindividual examples, the reaction between the components may be carriedout at lower temperatures, for instance at temperatures ranging fromroom temperature up to the boiling temperature of the mass using-longerreaction periods and, in some cases, stronger catalysts and highercatalyst concentrations.

It also will be understood by those skilled in the art that my inventionis not limited to conensation products obtained by reaction of in ciflctriazinyl compound named in the above 11- iustrative examples. Thus,instead of alphadiamino s-triazinyl thio acetamido) beta-(chloroacetamido) ethane, I may use, for examle, the correspondingfluoro, iodo or bromo deacetamido) (halogeno acetamido) alkane oralkene, a (diamino s-triazinyl thio acetamido) ,(halogeno acetamido)benzene, toluene or other divalent aromatic hydrocarbon, or any othertriazine derivative (or mixture thereof) of the "kind embraced byFormula I, numerous examles of which have been given above and in mycopending application Serial No. 432,659.

In producing these new condensation, prodcts the choice of the aldehydeisdependent largely upon economic considerations and upon he particularproperties desired in the finished ehyde, propionaldehyde,butyraldehyde, metharolein, crotonaldehyde, octaldehyde, benzaldehyde,furfural, etc., mixtures thereof, or mixures of formaldehyde (orcompounds engenderng formaldehyde) with such aldehydes. ative examplesof aldehyde-addition products that may be used instead of the aldehydesthemselves are the monoand polys-(N carbinol) devatives, moreparticularly the monoand polyethylol derivatives of urea, thiourea,seienourea eas, selenoureas and iminoureas, monoand ly-(N-carbinol)derivatives of amides of poly-' carboxylic acids, e. g., maleic,itaconic, fumaric, adipic, malonic, succinic, citric, phthalic, etc.,

aminotriazoles, of the aminodiazines, etc. Particularly good results areobtained with active ethylene-containing bodies such as a methylol ea,more particularly monoand di-methylol ,ureas, and a methylol melamine,e. g., monoinethylol melamine and polymethyloi melamines (di-, tri-,tetra-, pentaand hexamethylol melamines). Mixtures of aldehydes'" andaldehyde-addition products may be emloyed, e. g.,, mixtures offormaldehyde and methylol compounds such, for instance, as dimethylolurea, .tri-methylol melamine, hexamethylol melamine, etc.

The ratio of the aldehydic reactant to the ,tr iazine derivative may bevaried over a wide range, but ordinarily the reactants are employed inan amount corresponding to at least one mol the aldehyde, specificallyformaldehyde, for each moi of the triazine derivative. Thus, I may use,for example, from 1 to 7 or 8 or more mols ve. Good results are obtainedin manufacturlng thermosetting resinous compositions using pm about 2 to4. mols aldehyde, specifically tive. When the aldehyde is available forreacon in the form of an alkylol derivative, more particularly amethylol derivative such, for instance, as dimethylol urea,trimethyloimelamine, etc., then higher amounts of such aldehyde-additionproducts areemployed, for. instance from 2o! 3 up to 12 or 15 or moremols of such allol derivatives for each mol of the triazine derivative.

Illusonoand poly-(N-carbinol) derivatives of the 1 formaldehyde, foreach moi of triazine derivaredients comprising an aldehyde and the spe-fvatives, or other (diamino s-triazinyl thio As indicated hereinbefore,and as further shown by a number of the examples, the properties of thefundamental resins of this invention may bevaried widely by introducingother modifying bodies before, during or after effecting condensationbetween the primary components. Thus, as modifying agents 1 may use, forinstance,

monohydric alcohols such as ethyl, propyl, isopropyl, isobutyl, hexyl,etc., alcohols; polyhydric alcohols such as diethyleneglycol,triethylene glycol, pentaerythritol, etc.; alcohol-ethera'e. g.,

. thylene glycol monomethyl ether, ethylene glycol monoethyl ether,ethylene glycol monobutyl ether, ethylene glycol monophenyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,dlethylene glycol monobutyl I ether, etc.; amides such as formamide,stearamide, acrylamide, benzene'sulfonamides, toluene sulfonainides,adipic diamide,phthalic' diamide, etc.; amines, e.- g., ethylenediamine, phenylene diamine, etc.; phenol and substituted phenols,includingaminophenols, eta; ketones,

. including halogenated ketones; nitriles, including halogenatednitriles, e. g., acrylonitrile, methacrylonitrile, succinonitrile,chloroacetonitriles, etc.;acylated ureas, including halogenated acylated ureas of the kind'described, for example. in my Patent No.2,281,559, issued May 5, 1942;

, andothers.

d iminourea and of substituted ureas, thio- The modifying bodies alsomay take the form of high molecular weight bodies with or withoutresinous characteristics, for example, hydrolyzed woodproducts,formalized cellulose derivatives, lignin, protein-aldehyde condensationproducts, aminotriazole-aldehyde condensation products,aminodiazine-aidehyde condensation products, etc. Other examples ofmodifying bodies are the melamine-aldehyde condensation products,

- condensation products, phenol-aldehyde condensation products, modifiedor unmodified, saturated or unsaturated polyhydric'alcohol-polycarboxylicacid. condensation products, water-solublecellulose derivatives, natural gums and resins V such as shellac, rosin,etc.; polyvinyl compounds such as polyvinyl esters; e. g., polyvinylacetate, polyvinyl butyrate ietcn polyvinyl ethers, including polyvinylacetals, specifically polyvinyl formal, etc. I

Instead of effecting reaction between a triazine derivative of the kindembraced by Formula I plan aldehyde for each mol of triazine derivaandan aldehyde, specifically formaldehyde, I may cause an aldehyde tocondense with a salt. (organic or inorganic) of the triazine derivativeor with a mixture of the triazlne derivative and a Dyes, pigments,plasticizers, mold lubricants,

opacifiers and various fillers (e. g., wood flour, glass fibers,asbestos, including deflbrated asbes tos, mineral wool, mica, clothcuttings,-'etc.). may

be compounded with the resin in accordance with i conventional practiceto provide various thermoplastic and thermosetting molding compositions.

The modified and unmodified resinous compositions of this invention havea wide variety of uses. For example, in addition to their use in theproduction of molding compositions, they may be used as modifiers ofother natural and synthetic resins, as laminating varnishes in theproduction of laminated articles wherein sheet materials, e. g., paper,cloth, sheet asbestos, etc., are coated and impregnated with the resin,superimposed and thereafter united under heat and pressure. They may beused in the pro-' duction of wire and baking enamels from whichinsulated wires and other coated products are made, for bonding orcementing together mica flakes to form a laminated mica art'cle, forbonding together abrasive grains in the production of resin-bondedabrasive articles such, for. instance, as grindstones, sandpapers, etc.,in the manufacture of electrical resistors, etc. They may be used fortreating cotton, linen and other cellulosic materials in sheet or otherform. They also may be employed as impregnant's for electrical coils andfor other electrically insulating applications.

What I claim as new and desire to secure by Letters Patent of the UnitedStates is:

1. A composition of matter comprising the product of reaction ofingredients comprising an aldehyde and a compound corresponding to thegeneral formula where n represents an integer and is at least 1 and notmore than 2, Z represents a member of the class consisting of oxygen andsulfur, R represents a member of the class consisting of hydrogen andmonovalent hydrocarbon and halohydrocarbon radicals, R represents amember of the class consisting of divalent hydrocarbon andhalo-hydrocarbon radicals, and X represents a halogen atom.

2. A composition as in claim 1 wherein the aldehyde is formaldehyde.

3. A composition as in claim 1 wherein the reaction product is analkaline-catalyzed reaction product of the stated components.

4. A composition as in claim 1 wherein R represents a hydrogen atom.

5. A composition as in claim 1 wherein the reaction product is analcohol-modified reaction product of the stated components.

6. A composition of matter comprising the product of reaction ofingredients comprising an aldehyde and a compound corresponding to thegeneral formula where n represents an integer and is at least 1 and notmore than 2, 2 represents a member of the class consisting of oxygen andsulfur, R represents a member of the classconsisting of hydrogen andmonovalent hydrocarbon and halohydrocarbon radicals, R represents amember of the class consisting of divalent hydrocarbon andhalo-hydrocarbon radicals, and X represents a halogen atom.

A heat-curable resinous composition comprising a heat-convertiblecondensation product' of ingredients comprising formaldehyde and a.compound corresponding to the general formula IIIH:

where n represents an integer and is at least 1 and not more than 2, Zrepresents a member of the class consisting of oxygen and sulfur, Rrepresents a member of the class consisting of divalent hydrocarbon andhalo-hydrocarbon radicals, and X represents a halogen atom.

8. A product comprising the cured resinous. composition of claim 7.

- 9. A composition as in claim 7 wherein Z represents oxygen and Xrepresents chlorine.

10. A composition comprising a condensation product of ingredientscomprising an aldehyde and a (diamino s-triazinyl thio acetamido)(halogeno acetamido)-substituted aliphatic hydrocarbon.

11. A composition comprising a condensation product of ingredientscomprising an aldehyde and a (diamino s-triazinyl thio acetamido)(chloroacetamido) alkane.

12. A resinous composition comprising the product of reaction ofingredients comprising formaldehyde and alpha-(diamino s-triazinyl thioacetamido) beta-(chloroacetamido) ethane.

13. A composition comprising a condensation product of ingredientscomprising an aldehyde and a (diamino s-triazinyl thio acetamido)(halogeno acetamido)-substituted aromatic hydrocarbon.

14. A composition of matter comprising the product of reaction ofingredients comprising a urea, an aldehyde and a compound correspondingto the general formula NHR where n represents an integer and is at least1 and not more than 2, Z represents a member of the class consisting ofoxygen and sulfur, R represents a member of the class consisting ofhydrogen and monovalent hydrocarbon and halohydrocarbon radicals, Rrepresents a member of the class consisting of diyalent hydrocarbon andhalo-hydrocarbon radicals, and X represents a halogen atom.

15. A composition as in claim 14 wherein R represents hydrogen, thealdehyde is formaldehyde and the urea component is the compoundcorresponding to the formula NHaCONHz.

16. A composition comprising the resinous product of reaction ofingredients comprising urea, formaldehyde and alpha-(diamino s-triazinylthio acetamido) beta-(chloroacetamido) ethane.

17. A resinous composition comprising the product of reaction ofingredients comprising dimethylol urea and alpha-(diamino s-triazinylthio acetamido) beta-(chloroacetamido) ethane.

.18. A composition of matter comprising the product of reaction ofingredients comprising 'amido) ethane.

melamine, an aldehyde and a compound corresponding to the generalformula x na c II II ('3-s0.R,,.-c-NH-R'-NHco.R1.x

. .N p where n represents an integer and is at least 1 and not more than2, 2 represents a member of the class consisting of oxygen and sulfur, Rrep- 20. The method of preparing new synthetic compositions whichcomprises effecting reaction between ingredients comprising an aldehydeand a compound corresponding to the general formula where n representsan integer and is at least 1 and not more than 2, Z represents a memberof the class consisting of oxygen and sulfur, R represents a member ofthe class consisting of hydrogen and mon'ovalent hydrocarbon andhalohydrocarbon radicals, R represents a member of the class consistingof divalent hydrocarbon and halo-hydrocarbon radicals, and X representsahalogen atom.

GAEIANO F. DALELIO.

